This contribution describes a method to prepare high-capacity anion-exchange membranes for chromatographic bioseparations. Surface-initiated atom transfer radical polymerization was used to graft poly(2-dimethylaminoethyl methacrylate) (poly(DMAEMA)) nanolayers from the pore surfaces of commercially available regenerated cellulose membranes. Initial measurements were made to determine the thickness evolution of the poly(DMAEMA) nanolayers, using a model flat substrate designed to mimic the three-dimensional nature of initiator incorporation into the membrane. Thereafter, polymerization time was used as the independent variable to control the mass of polymer grafted from the membrane surfaces and, thus, the protein binding capacity. ATR-FTIR, AFM, and SEM were used to characterize changes in the chemical functionality, surface topography, and pore morphology of membranes as a result of modification. Bovine serum albumin was used to evaluate the static protein binding capacity of poly(DMAEMA)-modified membranes. Maximum static binding capacities increased with increasing polymerization time in a linear fashion for short polymerization times (<6h). For longer polymerization times, capacity increased non-linearly, eventually reaching a plateau value of 66.3 mg/mL. (c) 2008 Elsevier B.V. All rights reserved.